WO2004087577A1 - Fines particules de dioxyde de titane modifiees en surface, dispersion comprenant celles-ci, et procede de production desdites particules - Google Patents

Fines particules de dioxyde de titane modifiees en surface, dispersion comprenant celles-ci, et procede de production desdites particules Download PDF

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WO2004087577A1
WO2004087577A1 PCT/JP2004/004635 JP2004004635W WO2004087577A1 WO 2004087577 A1 WO2004087577 A1 WO 2004087577A1 JP 2004004635 W JP2004004635 W JP 2004004635W WO 2004087577 A1 WO2004087577 A1 WO 2004087577A1
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titanium dioxide
fine particles
modified titanium
dioxide fine
modified
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PCT/JP2004/004635
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English (en)
Japanese (ja)
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Shuji Sonezaki
Toshiaki Banzai
Koki Kanehira
Shinichi Yagi
Yumi Ogami
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Toto Ltd.
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Priority to EP04724741A priority Critical patent/EP1630136B1/fr
Priority to US10/551,071 priority patent/US20060264520A1/en
Priority to JP2005504273A priority patent/JP3775432B2/ja
Priority to AU2004226052A priority patent/AU2004226052B2/en
Publication of WO2004087577A1 publication Critical patent/WO2004087577A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides
    • C01G23/047—Titanium dioxide
    • C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K33/00—Medicinal preparations containing inorganic active ingredients
    • A61K33/24—Heavy metals; Compounds thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K41/00—Medicinal preparations obtained by treating materials with wave energy or particle radiation ; Therapies using these preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
    • A61P31/04—Antibacterial agents
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P35/00—Antineoplastic agents
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P43/00—Drugs for specific purposes, not provided for in groups A61P1/00-A61P41/00
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • B01J35/39—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/02—Oxides; Hydroxides
    • C01G49/06—Ferric oxide (Fe2O3)
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/0081—Composite particulate pigments or fillers, i.e. containing at least two solid phases, except those consisting of coated particles of one compound
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/36—Compounds of titanium
    • C09C1/3607—Titanium dioxide
    • C09C1/3676—Treatment with macro-molecular organic compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/30—Three-dimensional structures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/30—Treatment of water, waste water, or sewage by irradiation
    • C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/10—Photocatalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2991—Coated
    • Y10T428/2998—Coated including synthetic resin or polymer

Definitions

  • the present invention provides surface-modified titanium dioxide fine particles in which the surface of titanium dioxide is modified with a hydrophilic polymer having a carboxyl group, wherein the carboxyl group of the hydrophilic polymer and titanium dioxide are bonded by an ester bond.
  • the present invention relates to a surface-modified titanium dioxide fine particle, a dispersion thereof, and a method for producing the same. Background art
  • the isoelectric point of titanium dioxide is said to be around pH 6, so that titanium dioxide particles aggregate in an aqueous solvent near neutrality, making it extremely difficult to disperse them uniformly. . Therefore, various attempts have been made to date to uniformly disperse the titanium dioxide particles in an aqueous dispersion medium.
  • a nitric acid-oxidized titanium dioxide sol has been proposed in which a precipitate of titanium hydroxide is formed from titanium isopropoxide and peptized at high temperature under nitric acidity (eg, Chr i stophe, Barbeb: Journal).
  • H10-667516 by dispersing and stabilizing the titanium dioxide particles under a strong force by coating the surface of the particles with a porous silicon force.
  • a method for obtaining a dispersion of composite titanium dioxide fine particles for example, see Japanese Patent Application Laid-Open No. 11-13977
  • a method for improving dispersibility by containing a polycarboxylic acid or a salt thereof as a dispersant for example, a method of obtaining an aqueous solution of titanium dioxide (see, for example, Japanese Patent Application Laid-Open No. H02-212123) has been proposed.
  • particles in which a magnetic material and titanium dioxide are combined have been proposed.
  • particles having a surface coated with titanium alkoxide dissolved in an organic solvent using iron powder as a carrier see, for example, Japanese Patent Application Laid-Open No. H09-29980
  • iron oxide / silicone carrier Preparation of magnetic material and titanium dioxide composite particles by directly depositing amorphous or crystalline titanium dioxide by high temperature treatment (eg. Watson, Beydoun et al .: Journal of Photochemistry and Photobio Iogy A: Chemistry, 148, 303-313 (2002)).
  • the dispersant may be decomposed by the activity of the photocatalyst, and on the contrary, the activity of the photocatalyst may decrease.
  • problems such as aggregation and precipitation. Similar phenomena also occurred in composite particles with the above-mentioned magnetic material in which titanium dioxide was present on a part of the surface, and reagglomeration and sedimentation had become a problem.
  • titanium dioxide having a strong photoactivity resolution to a drug delivery system (DDS)
  • DDS drug delivery system
  • metal particles such as gold carrying titanium dioxide are shot into target cancer cells and taken in, and then irradiated with light such as ultraviolet rays to kill the cancer cells.
  • light such as ultraviolet rays to kill the cancer cells.
  • the activation of titanium dioxide can be controlled by turning light on and off, so its application to DDS for cancer treatment and the like is expected.
  • titanium dioxide is around pH 6 as described above. Under physiological conditions near neutrality, titanium dioxide particles still have a problem. For this reason, it has not been possible to directly administer the titanium dioxide dispersion as an injection solution into a blood vessel or use titanium dioxide particles as they are as a carrier for DDS. Disclosure of the invention
  • the present inventors have conducted intensive studies in order to solve the above-mentioned problems, and chemically modified a hydrophilic polymer on the surface of titanium dioxide fine particles to modify the surface.
  • the present inventors have found that the dispersibility in an aqueous solvent is extremely good even in the H region, and have completed the present invention. That is, the surface-modified titanium dioxide fine particles of the present invention have a hydrophilic polymer through an ester bond on the surface thereof, and are extremely good even in an aqueous solvent having a wide pH range as well as near neutrality. It shows excellent dispersibility.
  • a dispersion of surface-modified titanium dioxide particles utilizing this characteristic can be used as a solvent with various pH buffers containing water or salt, and is a stable dispersion having extremely good dispersibility.
  • the method for producing the surface-modified titanium dioxide fine particles of the present invention comprises mixing a titanium dioxide particle dispersion of 2 to 200 nm and a water-soluble polymer solution. The mixture is heated at 80 to 220 ° C. It is characterized by purifying surface-modified titanium dioxide particles by removing unbound water-soluble polymers after ester-bonding both.
  • the resulting surface-modified titanium dioxide fine particles of the present invention can be dispersed in an aqueous solvent not only neutral but also in a wide pH range, and are extremely stable against pH fluctuation and salt addition. It is.
  • it is easy to form a composite with other functional substances it is effective for producing particles having a new function.
  • the surface-modified titanium dioxide fine particles of the present invention are directly introduced into a lesion in the body and irradiated with light such as ultraviolet rays, so that cancer tissue and the like can be efficiently destroyed because aggregation does not occur.
  • various organic substances and microorganisms can be decomposed by irradiating ultraviolet rays or sunlight to induce a redox effect of the photocatalytic ability.
  • FIG. 1 is a schematic view showing the surface-modified titanium dioxide fine particles of the present invention.
  • FIG. 2 shows the photocatalytic activity of the surface-modified titanium dioxide fine particles of the present invention (methylenebutane).
  • FIG. 6 is a diagram showing the results of measurement of the absorbance due to the decomposition of roux (displayed as a decrease in absorbance).
  • ⁇ , ⁇ , ⁇ , ⁇ , and ⁇ represent the polyacrylic acid-bound titanium dioxide fine particles (anatase type) prepared in Examples 1 to 5, respectively.
  • FIG. 3 is a graph showing the cell killing of cancer cells by the photocatalytic activity of the surface-modified titanium dioxide particles of the present invention.
  • FIG. 1 is a schematic view showing the surface-modified titanium dioxide fine particles of the present invention.
  • the surface-modified titanium dioxide fine particles 1 of the present invention have a hydrophilic polymer 2 on the surface of titanium dioxide fine particles, and the carboxyl group of the hydrophilic polymer 2 and titanium dioxide are bonded by an ester bond. It is assumed that. In other words, the titanium dioxide on the surface of the titanium dioxide fine particles 1 is hydrated by water in the reaction system to form hydroxyl groups, and the hydroxyl groups react with the carboxyl groups of the hydrophilic polymer to form ester bonds.
  • Ru can be applied various analytical methods, for example by infrared spectroscopy in the presence or absence of the infrared absorption of 1 7 0 0 ⁇ 1 8 0 0 cm _ 1 near the absorption bands of the ester bond It is possible to confirm.
  • the isoelectric point of the surface-modified titanium dioxide particles becomes close to the isoelectric point (pH 2.8 to 2.9) of the carboxyl residue of the hydrophilic polymer, Even in a solvent, an electric repulsion acts between the particles, so that the particles exhibit good dispersibility.
  • the titanium dioxide particles used in the present invention may have an anadase type or a rutile type crystal system. This is because even if the crystal systems are different, the surface modification is possible if the chemical properties of hydration and generation of hydroxyl groups are the same. If a strong photocatalytic activity is desired, the anatase type can be suitably selected, and if a property such as a high refractive index such as a cosmetic is desired, the rutile type can be suitably selected. For the same reason, not only single titanium dioxide particles but also composite titanium dioxide particles composed of titanium dioxide and a magnetic material are preferably used. Further, from the viewpoint of the degree of freedom of the form of use, it is desirable that these dispersed particle diameters are 2 to 200 nm. This is because when the particle size is larger than 200 n, the effect of the gravity acting on the fine particles increases, and the particles are more likely to settle.
  • the surface-modified titanium dioxide fine particles of the present invention are characterized in that the hydrophilic polymer is a water-soluble high molecule.
  • the hydrophilic polymer is a water-soluble high molecule.
  • a water-soluble polymer is preferable as the hydrophilic polymer used in the present invention. That's why.
  • Any water-soluble polymer having a plurality of carboxyl groups can be used.Examples include carboxymethyl starch, carboxymethyl dextran, carboxymethyl cellulose, polycarboxylic acids, and copolymers having a carboxyl group unit. (Copolymer) and the like.
  • a copolymer of polycarboxylic acids such as polyacrylic acid and polymaleic acid
  • a copolymer of acrylic acid / maleic acid / acrylic acid / nosulfonate monomer Is more preferably used.
  • the dispersion liquid of the surface-modified titanium dioxide particles of the present invention is characterized in that the surface-modified titanium dioxide particles are dispersed in an aqueous solvent. This is because, in an aqueous dispersion medium, the protons of the carboxyl residues present on the surface of the surface-modified titanium dioxide fine particles are in a dissociated state. By being stable for a long time without doing Moreover, it is basically extremely stable against pH fluctuation and addition of inorganic salts. Further, the isoelectric point of the surface-modified titanium dioxide fine particles of the present invention is determined by the carboxyl residue of the hydrophilic polymer. Is near the isoelectric point (PH 2.8 to 2.9).
  • Suitable buffers that can be used here include glycine buffer, acetate buffer, phosphate buffer (including PBS), carbonate buffer, pine quinbaine buffer, good buffer, boric acid. Buffers and the like can be mentioned. The ability to use near neutral buffers is extremely advantageous for applications in the biotechnology and pharmaceutical and medical fields.
  • the carboxyl group / titanium dioxide content ratio (m 0 I / g) of the surface-modified titanium dioxide fine particles in the dispersion varies depending on the reaction conditions, but is generally about 2 ⁇ 1 0 3 or more at which the is not preferable.
  • the method for producing surface-modified titanium dioxide fine particles of the present invention comprises: (1) a step of dispersing a titanium dioxide sol in a solvent in a reaction of binding a hydrophilic polymer to the surface of titanium dioxide fine particles; (3) a step of mixing these dispersions, (4) a step of heating this mixture, and (5) a step of dissolving the surface-modified titanium dioxide fine particles. It is characterized by comprising a step of separating the hydrophilic polymer and a step of purifying the surface-modified titanium dioxide fine particles.
  • the solvent used in (1) and (2) is preferably a solvent that can dissolve both the titanium dioxide sol and the hydrophilic polymer. This is because, when titanium dioxide aggregates in a solvent, the surface area where a binding reaction with a hydrophilic polymer can occur is reduced, so that the dispersion particle diameter in an aqueous solvent after the reaction is increased and the dispersibility is also deteriorated. is there. Further, a solvent having reactivity with the surface of the titanium dioxide particles is not suitable as the solvent used here.
  • alcohols containing a hydroxyl group form an ether bond with the surface of the titanium dioxide particles when heated, and thus inhibit the bonding reaction with the desired hydrophilic polymer.
  • the surface characteristics of the titanium dioxide particles depend on the characteristics of the alcohol used, and the dispersibility of the titanium dioxide particles in an aqueous dispersion medium is significantly reduced.
  • the solvent used in the present invention is preferably a non-protonic polar solvent such as dimethylformamide, dioxane, or dimethylsulfoxide from the above-mentioned reactivity point of view, but from the viewpoint of the volatility of the solvent. More preferably, dimethylformamide is used.
  • a titanium dioxide dispersion of the solvent and a hydrophilic polymer dispersion are mixed and stirred to prepare a dispersion in which titanium dioxide and the hydrophilic polymer are uniformly dispersed.
  • a hydrophilic polymer is directly added to the titanium dioxide dispersion, aggregation of the titanium dioxide may be caused. Therefore, it is preferable that each dispersion is prepared and then mixed.
  • the mixed solution is heated to perform a binding reaction.
  • the reaction proceeds without applying pressure.
  • polyacrylic acid plain
  • the final concentration of polyacrylic acid is preferably set to 0.4 mg ZmI or more in order to improve the dispersibility.
  • the heating temperature is 80 to 220 ° C.
  • the heating temperature is 80 ° less than a C dispersibility in an aqueous solvent bonding of the hydrophilic polymer is lowered is lowered.
  • the reaction is performed under pressure, if the heating temperature exceeds 220 ° C., it is unsuitable due to the problem of the tightness of the reaction vessel.
  • the reaction proceeds at a temperature equal to or higher than the boiling point of water, the titanium dioxide aggregates when the water contained in the titanium dioxide sol is completely volatilized out of the reaction system. Is desirable.
  • the water content in the reaction solution is too high, the reaction may be adversely affected. Therefore, the water content in the reaction solution depends on the reaction conditions, but is preferably approximately 4% or less.
  • the generated surface-modified titanium dioxide fine particles and the unbound hydrophilic polymer are separated.
  • a dialysis method, an ultrafiltration method, a gel filtration chromatography method, a precipitation method, or the like can be suitably used, but when the separation is performed by a dialysis method or an ultrafiltration method, the hydrophilicity used is high. It is necessary to use a dialysis or ultrafiltration membrane that matches the molecular weight of the molecule. That is, although separation can be performed by any of the above methods, it is desirable to use a precipitation method because of the simplicity of the operation.
  • the precipitation method includes a method using an isoelectric point and a method using salting out. Any of them can be suitably used.
  • the reaction solvent is removed under reduced pressure in an evaporator, water is added, and the mixture is stirred to disperse the surface-modified titanium dioxide fine particles.
  • an inorganic acid is added to the dispersion to lower the pH of the dispersion to 2.8 or less.
  • the surface-modified titanium dioxide loses negative charges on the surface and agglomerates.
  • the hydrophilic polymer that is not bonded to the particles remains in the dispersion without aggregating. It is possible to remove unbound hydrophilic polymer with care.
  • the reaction solution is collected in a separating funnel after completion of the reaction.
  • An organic solvent which separates with water is added, followed by stirring and mixing.
  • the aqueous layer contains the surface-modified titanium dioxide
  • the organic solvent layer contains the non-protonic organic solvent used in the reaction.
  • the precipitated surface-modified titanium dioxide fine particles are washed with water, and then the surface-modified titanium dioxide fine particles are dissolved in an aqueous solvent having a pH of 3 to 13, preferably pH 5 to 12. Suspend.
  • an aqueous solvent having a pH of 3 to 13, preferably pH 5 to 12.
  • water, a desired pH buffer, or an alkaline aqueous solution can be suitably used.
  • the surface-modified titanium dioxide fine particles are uniformly dispersed by stirring or ultrasonic irradiation of this suspension, and then dried after desalting to obtain a dry powder of the surface-modified fine titanium dioxide particles.
  • the ability to produce stable powders that are easy to handle is extremely advantageous when applying surface-modified titanium dioxide fine particles to various uses.
  • composite titanium dioxide fine particles composed of titanium dioxide and a magnetic material
  • the characteristics in a solvent are similar to a single titanium dioxide.
  • the same production method and purification method as described above can be applied. Since the surface-modified composite titanium dioxide fine particles have magnetism, they are extremely useful because they can be easily recovered by a magnet after the treatment, for example, when applied to the decomposition treatment of harmful substances in water.
  • This dispersion was placed in a 100-ml vial, and sonicated at 200 Hz for 30 minutes.
  • the average dispersed particle diameters before and after the ultrasonic treatment were 36.4 nm and 20.2 nm, respectively.
  • the solution was concentrated to prepare a titanium dioxide sol having a solid component of 20%.
  • the resulting titanium dioxide sol, 0-75 mI was dispersed in 20 mI of dimethylformamide (DMF), and polyacrylic acid (average molecular weight: 500,000, Wako Pure Chemical Industries) 0.3 After adding 10 ml of DMF in which g was dissolved, the mixture was stirred and mixed.
  • DMF dimethylformamide
  • polyacrylic acid average molecular weight: 500,000, Wako Pure Chemical Industries
  • the solution was transferred to a hydrothermal reaction vessel (HU-50, San-ai Science), and synthesis was performed at 180 ° C for 6 hours. After the completion of the reaction, the reaction vessel was cooled to a temperature of 50 ° C. or less, and after taking out the solution, 120 ml of water was added and mixed with stirring. After removing DMF and water by evaporation, 20 ml of water was added again to obtain a polyacrylic acid-bound titanium dioxide aqueous solution. Unreacted polyacrylic acid was separated by adding 1 ml of 2N hydrochloric acid to precipitate polyacrylic acid-bound titanium dioxide fine particles and removing the supernatant after centrifugation.
  • a hydrothermal reaction vessel HU-50, San-ai Science
  • Polyacrylic acid-bonded titanium dioxide fine particles were produced in exactly the same manner as in Example 1, except that STS-01 of nitric acid anatase sol (Ishihara Industrial Co., Ltd., solid content: 20%) was used as the titanium dioxide sol.
  • STS-01 of nitric acid anatase sol Ishihara Industrial Co., Ltd., solid content: 20%
  • the dispersion particle diameter of the prepared polyacrylic acid-bound titanium dioxide fine particles was measured and found to be 66.6 nm.
  • the obtained aqueous solution of polyacrylic acid-bound titanium dioxide was desalted with a desalting column PD 10 and then dried at 100 ° C. to obtain polyacrylic acid-bound titanium dioxide fine particles (anatase type).
  • polyacrylic acid-bound titanium dioxide fine particles were synthesized in exactly the same manner as in Example 2 to obtain an aqueous solution of polyacrylic acid-bound titanium dioxide having a solid content of 1.5%. .
  • the dispersion particle size of the prepared polyacrylic acid-bonded titanium dioxide fine particles was measured and found to be 66. 6 nm.
  • the obtained aqueous solution of polyacrylic acid-bound titanium dioxide is desalted with a desalting column PD 10 and then dried at 100 ° C. to obtain polyacrylic acid-bound titanium dioxide fine particles (Anarose type). Got.
  • Polyacrylic acid-bonded titanium dioxide fine particles were synthesized in exactly the same manner as in Example 2 except that the synthesis temperature was set to 130 ° C., to obtain an aqueous solution of polyacrylic acid-bonded titanium dioxide having a solid content of 5.5%. .
  • the dispersion particle size of the prepared polyacrylic acid-bonded titanium dioxide fine particles was measured to be 67.4 nm.
  • the obtained aqueous solution of polyacrylic acid-bound titanium dioxide was desalted with a desalting column PD 10 and dried at 100 ° C. to obtain polyacrylic acid-bound titanium dioxide fine particles (anatase type).
  • Polyacrylic acid-bonded titanium dioxide fine particles were synthesized in exactly the same manner as in Example 2 except that the synthesis temperature was set to 80 ° C., to obtain a 1.5% solid component aqueous solution of polyacrylic acid-bound titanium dioxide.
  • the dispersion particle size of the prepared polyacrylic acid-bonded titanium dioxide fine particles was measured to be 67.9 nm.
  • the obtained aqueous solution of polyacrylic acid-bound titanium dioxide was desalted with a desalting column PD 10 and dried at 100 ° C. to obtain polyacrylic acid-bound titanium dioxide fine particles (anatase type).
  • a mixture of 3.6 g of titanium tetraisopropoxide and 3.6 g of isopropanol was added dropwise to 60 ml of ultrapure water under ice cooling to carry out hydrolysis. After the dropwise addition, the mixture was stirred at room temperature for 30 minutes. After stirring, 12 ml of 1N nitric acid was added dropwise at 80 ° C for 8 hours. The mixture was stirred for a while, and the mixture was subjected to a petition. After completion of the filtration, the solution was filtered through a 0.45 m filter, and the solution was exchanged using a desalting column PD10 to prepare a titanium dioxide sol having a solid content of 1%.
  • This dispersion was placed in a 100 ml vial and sonicated at 200 Hz for 30 minutes.
  • the average dispersed particle diameters before and after sonication were 36.4 nm and 20.2 nm, respectively.
  • the solution was concentrated to prepare a titanium dioxide sol having a solid component of 20%. 0.75 mI of the obtained titanium dioxide sol is dispersed in 20 mI of dimethylformamide (DMF), and 0.3 g of polyacrylic acid (average molecular weight: 500, Wako Pure Chemical Industries) is dissolved. After adding 10 mI of DMF, the mixture was stirred and mixed.
  • DMF dimethylformamide
  • polyacrylic acid average molecular weight: 500, Wako Pure Chemical Industries
  • the solution was transferred to a hydrothermal reactor (HU-50, San-ai Science), and synthesis was performed at 180 ° C for 6 hours. After the completion of the reaction, the reaction vessel was cooled to a temperature of 50 ° C. or lower, and the solution was taken out into a separating funnel. Next, 40 ml of porcine mouth was added, and the mixture was stirred and mixed. Then, the lower layer was removed, and the upper layer was recovered. This step was repeated twice to remove DMF. To 10 ml of this solution was added 10 ml of 1.5 M NaCI and 20% (w / v) polyethylene glycol 600 (Wako Pure Chemical Industries, Ltd.). Removed.
  • This dispersion was placed in a 100 ml vial and sonicated at 200 Hz for 30 minutes.
  • the average dispersed particle diameters before and after sonication were 36.4 nm and 20.2 nm, respectively.
  • the solution was concentrated to prepare a titanium dioxide sol having a solid component of 20%. 0.75 mI of the obtained titanium dioxide sol was dispersed in 20 mI of dimethylformamide (DMF), and 0.3 g of polyacrylic acid (average molecular weight: 500, Wako Pure Chemical Industries) was dissolved. After adding 10 mI of DMF, the mixture was stirred and mixed.
  • DMF dimethylformamide
  • the solution was transferred to a hydrothermal reactor (HU-50, San-ai Science), and synthesis was performed at 150 ° C for 5 hours. After the completion of the reaction, the reaction solution was cooled until the temperature of the reaction vessel became 50 ° C or less. To the reaction solution, twice the amount of isopropanol (Wako Pure Chemical Industries) was added. After standing at room temperature for 30 minutes, the precipitate was recovered by centrifugation. After the collected precipitate was was washed with 70% ethanol, 2.5 ml of water was added to obtain a dispersion of polyacrylic acid-bound titanium dioxide fine particles (anatase type).
  • Polyacrylic acid-bonded titanium dioxide fine particles were synthesized in exactly the same manner as in Example 7, except that polyacrylic acids having average molecular weights of 2000 and 350 were used. Even when polyacrylic acids having average molecular weights of 2000 and 350 were used, the dispersions of the polyacrylic acid-bound titanium dioxide fine particles (anatase type) were both favorable and showed good dispersibility.
  • titanium tetraisopropoxide (Wako Pure Chemical Industries) was added to a final concentration of 5 mM.
  • the aqueous solution was centrifuged and the precipitate was calcined at 350 ° C for 2 hours. After firing, the mixture was dispersed in a 1 OmM aqueous solution of nitric acid, sonicated, and filtered through a 0.1 / Im filter.
  • Example 7 0.75 ml of a 20% titanium dioxide sol having a solid content obtained in the process of Example 7 was dispersed in 1 O ml of DMF, and different weights of polyacrylic acid (average molecular weight: 500,000 After adding 5 ml of a DMF solution containing (Koujunyaku), the mixture was stirred and mixed. The solution was transferred to a hydrothermal reaction vessel (HU-50, San-ai Science), and synthesis was performed at 150 ° C for 5 hours. After completion of the reaction, the properties of each solution were observed However, when the final concentration of polyacrylic acid was 0.4 mgZml or more, a dispersion of well-dispersed polyacrylic acid-bound titanium dioxide fine particles was obtained.
  • the concentration of polyacrylic acid was lower than this, the dispersion was opaque but opaque and the particle size was large. Therefore, it was found that under the above reaction conditions, the final concentration of polyacrylic acid was required to be 0.4 mg / mI or more.
  • the water content during the reaction is preferably 4% or less as the final concentration.
  • a solution (A) of 1 g of polyacrylic acid dissolved in 1 O ml of DMF was used. Titanium dioxide sol with a solid content of 20% obtained in the process of Example 7. A solution in which 25 ml was dispersed in 1 O ml of DMF was used as a solution (B). Further, 0.25 mI of a 20% solid component titanium dioxide sol obtained in the process of Example 7 and 1 g of 20% (w / V) polyacrylic acid were dispersed in 1 OmI DMF. This was used as a solution (C). Furthermore, a dispersion of polyacrylic acid-bound titanium dioxide fine particles obtained by reacting the solution (C) at 150 ° C.
  • solution (D) since the surface of titanium dioxide is modified with numerous carboxyl residues, the isoelectric point of the whole fine particles is around pH 2.8, and they are uniformly dispersed even in a neutral solution. The state is kept. That is, from the results of Examples 13 and 14 in the comparison between the solutions (C) and (D), the polyacrylic acid-bonded silicon dioxide fine particles were in a state where the dispersibility was simply increased by the addition of polyacrylic acid. It was found that the titanium dioxide particles showed completely different physical properties.
  • the polyacrylic acid-bound titanium dioxide fine particles obtained in Examples 1 to 7 were dispersed in water, and the pH of the solution was changed from pH 3 to pH 13 in steps of pH 1 using hydrochloric acid and sodium hydroxide. Then, it was observed whether aggregation or precipitation of the polyacrylic acid titanium dioxide fine particles occurred.
  • the aqueous solution with the changed pH was centrifuged at 400 rpm to confirm the presence or absence of aggregation, but no aggregation or precipitation of each particle was observed at any pH.
  • FT-IR Infrared spectroscopy
  • Example 7 The polyacrylic acid-bound titanium dioxide fine particle dispersion obtained in Example 7 was heated and dried at 110 ° C. for 1 hour, and then slightly more than 4 hours. Heated to complete incineration. This was cooled in a silica gel desiccator, and the mass was measured as the net amount of titanium dioxide in the dispersion. The results indicated that the dispersion contained 8.82% (w / V) titanium dioxide.
  • the polyacrylic acid-bound titanium dioxide fine particles (anatase type) obtained in Examples 1 to 5 were mixed with 50 mM phosphate buffer (pH 7.0) so that the solid content was 0.02%. Diluted. Methylene blue trihydrate (Wako Pure Chemical Industries) was added to the aqueous solution to a concentration of 40M. While stirring, this aqueous solution was irradiated with ultraviolet light having a wavelength of 340 nm to 1.5 mW / cm 2, and the absorption at a wavelength of 580 nm was measured with an ultraviolet-visible light spectrophotometer. . The results are shown in FIG.
  • the polyacrylic acid-bound titanium dioxide fine particles (anatase type) obtained in Example 1 were adjusted with 50 mM phosphate buffer (pH 7.0) so that the solid content was 1.0%. After inoculating Escherichia coli and culturing overnight at 37 ° C in B broth, the culture is centrifuged, and the cells are washed with 50 mM phosphate buffer (pH 7.0). The suspension was suspended in an amount of 50 mM phosphate buffer (pH 7.0). This was further diluted 100-fold with a 50-m phosphate buffer (pH 7.0) and used as the test bacterial solution. ⁇ The polyacrylic acid-bound titanium dioxide fine particles were added to the test bacterial solution at the final concentration.
  • test solution Place a mixture of the test bacterial solution and polyacrylic acid-bound titanium dioxide fine particles in a small petri dish to a depth of 3 mm. The plate was allowed to stand at room temperature under black light irradiation (dose: 900 / W / cm 2 ). In addition, a sample to which no polyacrylic acid-bound titanium dioxide fine particles were added was irradiated with black light similarly as Control 1. A part of the test solution was collected before irradiation, 2 hours after irradiation, and 4 hours after irradiation, and the number of bacteria was counted according to a conventional method using LB agar medium.
  • the polyacrylic acid-bound titanium dioxide fine particles (anatase type) obtained in Example 1 were adjusted with a PBS buffer (pH 6.8) so that the solid content was 1.0%.
  • Two types of cultured cancer cells (Raj ⁇ , Jurkat) were cultured in RPMI 1640 medium (manufactured by GIBCO) containing 10% serum at 37 ° C and 5% carbon dioxide atmosphere. 5. to prepare a cell solution of 8 X 1 0 5. This was cultured again under the same conditions for 20 hours to obtain a test cell solution.
  • the above polyacrylic acid-bound titanium dioxide fine particle dispersion was added to a final concentration of 0.1%. And used as a test solution.
  • test solution was poured into a small petri dish so as to have a liquid depth of 3 mm, and allowed to stand at room temperature under irradiation with black light (UV) (dose: 900 W / cm 2 ).
  • UV black light
  • blanks (untreated) that did not add polyacrylic acid-bound titanium dioxide fine particles and did not irradiate UV, those that did not irradiate UV after adding polyacrylic acid-bound titanium dioxide fine particles, and those that did not irradiate UV The test was performed at the same time, with the control simply irradiated with UV light without adding fine particles. Six hours later, each test solution was collected, and the number of each cell was counted.
  • Figure 3 shows the results. In the system where polyacrylic acid-bound titanium dioxide particles were added and the cells were irradiated with UV light, the number of cells decreased drastically, indicating that the polyacrylic acid-bound titanium dioxide particles have cell killing properties against cancer cells. Admitted. Industrial applicability
  • surface-modified titanium dioxide fine particles having excellent dispersibility in a neutral aqueous solvent suitable for various applications, and having long-term stable dispersibility even in a wide pH range, and a dispersion thereof, And a method for manufacturing the same.

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Abstract

L'invention concerne des fines particules de dioxyde de titane, modifiées en surface, présentant une surface chimiquement modifiée par un polymère hydrophile, caractérisées en ce qu'un groupe carboxyle du polymère hydrophile et le dioxyde de titane sont liés par une liaison ester. L'invention concerne en outre un procédé de production de fines particules de dioxyde de titane modifiées en surface, caractérisé en ce qu'on mélange une dispersion comprenant des fines particules de dioxyde de titane, de granulométrie de 2 à 200 nm, avec une solution d'un polymère hydrosoluble, en ce qu'on chauffe le mélange résultant à une température de 80 à 220 °C, de façon à lier les composants par une liaison ester, et en ce qu'on élimine le polymère hydrosoluble non lié, pour purifier les particules résultantes. Les fines particules de dioxyde de titane modifiées en surface présentent une excellente dispersibilité et stabilité dans un solvant aqueux couvrant une vaste plage de pH, y compris une plage neutre.
PCT/JP2004/004635 2003-03-31 2004-03-31 Fines particules de dioxyde de titane modifiees en surface, dispersion comprenant celles-ci, et procede de production desdites particules WO2004087577A1 (fr)

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EP04724741A EP1630136B1 (fr) 2003-03-31 2004-03-31 Fines particules de dioxyde de titane modifiees en surface, dispersion comprenant celles-ci, et procede de production desdites particules
US10/551,071 US20060264520A1 (en) 2003-03-31 2004-03-31 Surface-modified titanium dioxide fine particles and dispersion comprising the same, and method for producing the same
JP2005504273A JP3775432B2 (ja) 2003-03-31 2004-03-31 表面改質二酸化チタン微粒子とその分散液、およびその製造方法
AU2004226052A AU2004226052B2 (en) 2003-03-31 2004-03-31 Surface-modified titanium dioxide fine particles and dispersion comprising the same, and method for producing the same

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JP2013104004A (ja) * 2011-11-15 2013-05-30 Toyota Industries Corp フィラーおよびその製造方法
WO2014141992A1 (fr) * 2013-03-15 2014-09-18 株式会社ダイセル Dispersion liquide d'oxyde de titane, revêtement liquide à base d'oxyde de titane, et film de revêtement pour photocatalyseur
WO2014148949A1 (fr) 2013-03-22 2014-09-25 Асави, Ллс Alkyl 2-{[(2r,3s,5r)-5-(4-amino-2-oxo-2n-pyrimidin-1-yl)-3-hydroxy-tétrahydro-furan-2-ilméthoxy]-phénoxy-phosphorilamino}-propionates, inhibiteurs de nucléosides d'arn-polymérase hcv ns5b, procédés de fabrication et d'utilisation
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JP2006213592A (ja) * 2005-01-06 2006-08-17 Hitachi Software Eng Co Ltd 半導体ナノ粒子表面修飾方法
WO2007018147A1 (fr) * 2005-08-05 2007-02-15 Toto Ltd. Matériau composite de dioxyde de titane pharmaceutique dont on peut supprimer l’effet pharmacologique par irradiation de lumière
JP2007063253A (ja) * 2005-08-05 2007-03-15 Toto Ltd 光照射により薬効を消失させる医薬二酸化チタン複合材
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US20150352227A1 (en) * 2006-03-24 2015-12-10 Toto Ltd. Method for accumulating titanium oxide composite particles into a cancer tissue
WO2007122956A1 (fr) * 2006-03-24 2007-11-01 Toto Ltd. Particules complexes d'oxyde de titane, dispersion des particules et procédé pour la production des particules
WO2009144775A1 (fr) 2008-05-29 2009-12-03 Toto株式会社 Agent anti-tumoral
WO2011058084A1 (fr) 2009-11-14 2011-05-19 F. Hoffmann-La Roche Ag Marqueurs biologiques destinés à prédire une réaction rapide au traitement du virus de l'hépatite c (hcv)
WO2011067195A1 (fr) 2009-12-02 2011-06-09 F. Hoffmann-La Roche Ag Biomarqueurs pour prédire une réponse soutenue à un traitement du vhc
JP2012056793A (ja) * 2010-09-09 2012-03-22 Seiko Epson Corp 有機修飾無機微粒子の製造方法
JP2013104004A (ja) * 2011-11-15 2013-05-30 Toyota Industries Corp フィラーおよびその製造方法
WO2014141992A1 (fr) * 2013-03-15 2014-09-18 株式会社ダイセル Dispersion liquide d'oxyde de titane, revêtement liquide à base d'oxyde de titane, et film de revêtement pour photocatalyseur
US9440221B2 (en) 2013-03-15 2016-09-13 Daicel Corporation Titanium oxide dispersion liquid, titanium oxide coating liquid, and photocatalyst coating film
JPWO2014141992A1 (ja) * 2013-03-15 2017-02-16 株式会社ダイセル 酸化チタン分散液、酸化チタン塗布液、及び光触媒塗膜
WO2014148949A1 (fr) 2013-03-22 2014-09-25 Асави, Ллс Alkyl 2-{[(2r,3s,5r)-5-(4-amino-2-oxo-2n-pyrimidin-1-yl)-3-hydroxy-tétrahydro-furan-2-ilméthoxy]-phénoxy-phosphorilamino}-propionates, inhibiteurs de nucléosides d'arn-polymérase hcv ns5b, procédés de fabrication et d'utilisation

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